Polyol compositions and rigid polyisocyanate based foams containing 2-chloropropane and aliphatic hydrocarbon blowing agents

ABSTRACT

There is provided a polyol composition which comprises a 
     a) compound having at least two isocyanate reactive hydrogens, at least one of which is a polyoxyalkylene polyether polyol, 
     b) 2-chloropropane, and, 
     c) a C 4  -C 6  aliphatic hydrocarbon. 
     There is also provided a rigid polyurethane foam made with the polyol composition. The 2-chloropropane acts to solubilize the C 4  -C 6  aliphatic hydrocarbon in the polyols.

This is a continuation of application Ser. No. 08/291,631 filed Aug. 17,1994 now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to polyol compositions and rigid polyisocyanatebased foams. In particular, the polyol composition and rigidpolyurethane foams made therewith are made with a combination of apolyoxyalkylene polyether polyol, 2-chloropropane and a C₄ -C₆ aliphatichydrocarbon blowing agent.

2. Background of the Invention

The polyurethane foam industry is well under way replacing the ozonedepleting chlorofluorocarbons (CFCs) with more benign compounds such ashydrochlorofluorocarbons (HCFCs). However, HCFCs appear to be atemporary replacement; and efforts continue toward a permanent solutionby employing blowing agents that have zero ozone depletion potential.

Hydrocarbons are a class of compounds receiving considerable attentionas possible permanent solutions to HCFC-blown foams. Advantages ofhydrocarbons include a zero ozone depletion potential, a very low globalwarming potential, and being liquids at more temperature. Hydrocarbonsare also inexpensive when compared to HCFCs or hydrofluoroalkanes(HFAs). In addition, the technology for the safe handling of flammableblowing agents in a manufacturing environment already exists inpractice. One drawback to hydrocarbons, however, is that they areinsoluble in polyols and do not form stable homogenous mixtures. Thisnot only leads to processing complications but also a nonuniform celldensity in the foam product. As a result, hydrocarbons must beseparately added and vigorously mixed with polyols immediately prior tothe manufacture of the rigid foam or injected as a separate stream intoa mix head. If one desires to avoid separate addition and mixing thepolyols and hydrocarbon immediately prior to foam manufacture, the onlyother solution currently is to create an emulsion using emulsifiers.

SUMMARY OF THE INVENTION

It is an object of the invention to make a polyol composition where a C₄-C₆ aliphatic hydrocarbon is homogeneously miscible with polyols used inthe manufacture of rigid polyisocyanate based foams. This object is madepossible by adding 2-chloropropane to the polyol composition. A polyolcomposition containing a C₄ -C₆ aliphatic hydrocarbon dissolved inpolyols by 2-chloropropane can be pre-manufactured and formulated as apackage suitable for transport to a manufacturer of rigid polyisocyanatebased foams.

DETAILED DESCRIPTION OF THE INVENTION

The polyol composition of the invention comprises a

a) compound having at least two isocyanate reactive hydrogens, at leastone of which is a polyoxyalkylene polyether polyol,

b) 2-chloropropane, and,

c) a C₄ -C₆ aliphatic hydrocarbon, optionally along with catalysts,chain extenders, additive flame retardants, surfactants, and fillers.The polyol composition is reacted with an organic isocyanate in thepresence of blowing agents.

The compounds with at least two isocyanate reactive hydrogens have afunctionality of 1.8 to 8, more preferably 3 to 8, and an averagehydroxyl number of 150 to 850, more preferably 350 to 800, and a numberaverage molecular weight of greater than 400. Polyols having hydroxylnumbers outside this range may be used, but it is preferred that theaverage hydroxyl number for the total amount of polyols used fall withinthe range of 150 to 850.

Examples include at least a polyoxyalkylene polyether polyol, andoptionally polythioether polyols, polyester amides and polyacetalscontaining hydroxyl groups, aliphatic polycarbonates containing hydroxylgroups, amine terminated polyoxyalkylene polyethers, or polyesterpolyols. In addition, mixtures of at least two of the aforesaid polyolscan be used.

Polyoxyalkylene polyether polyols, which is meant to include within itsscope the polymer modified polyols, are at least one of the compoundsused as the compounds having at least two isocyanate active hydrogens.To prepare the convention polyether polyols, any suitable alkylene oxidemay be used such as 1,3-propylene oxide, 1,2- and 2,3-butylene oxide,amylene oxides, styrene oxide, and preferably ethylene oxide and1,2-propylene oxide and mixtures of these oxides. The polyalkylenepolyether polyols may be prepared from other starting materials such astetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures;epihalohydrins such as epichlorohydrin; as well as aralkylene oxidessuch as styrene oxide. The polyalkylene polyether polyols may haveeither primary or secondary hydroxyl groups.

Included among the polyether polyols are polyoxyethylene glycol,polyoxypropylene glycol, polyoxybutylene glycol, polytetramethyleneglycol, block copolymers, for example, combinations of polyoxypropyleneand polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethyleneglycols, poly-1,4-tetramethylene and polyoxyethylene glycols, andcopolymer glycols prepared from blends or sequential addition of two ormore alkylene oxides. The polyalkylene polyether polyols may be preparedby any known process such as, for example, the process disclosed byWurtz in 1859 and Encyclopedia of Chemical Technology, Vol. 7, pp.257-262, published by Interscience Publishers, Inc. (1951) or in U.S.Pat. No. 1,922,459.

Polyethers include the alkylene oxide addition products of polyhydricalcohols such as ethylene glycol, propylene glycol, dipropylene glycol,trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1-trimethylol-propane, 1,1,1-trimethylolethane, pentaerythritol,1,2,6-hexanetriol, α-methyl glucoside, sucrose, and sorbitol. Alsoincluded within the term "polyhydric alcohol" are compounds derived fromphenol such as 2,2-bis(4-hydroxyphenyl)-propane, commonly known asBisphenol A.

Suitable organic amine initiators which may be condensed with alkyleneoxides include aromatic amines such as aniline,N-alkylphenylene-diamines, 2,4'-, 2,2'-, and 4,4'-methylenedianiline,2,6- or 2,4-toluenediamine, vicinal toluenediamines, o-chloro-aniline,p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, the variouscondensation products of aniline and formaldehyde, and the isomericdiaminotoluenes; and aliphatic amines such as mono-, di-, andtrialkanolamines, ethylene diamine, propylene diamine,diethylenetriamine, methylamine, triisopropanolamine,1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane. Preferableamines include monoethanolamine, vicinal toluenediamines,ethylenediamines, and propylenediamine.

Also suitable as the "polyoxyalkylene polyether polyol" as meant hereinare polymer modified polyols, in particular, the so-called graftpolyols. Graft polyols are well known to the art and are prepared by thein situ polymerization of one or more vinyl monomers, preferablyacrylonitrile and styrene, in the presence of a polyether or polyesterpolyol, particularly polyols containing a minor amount of natural orinduced unsaturation. Methods of preparing such graft polyols may befound in columns 1-5 and in the Examples of U.S. Pat. No. 3,652,639; incolumns 1-6 and the Examples of U.S. Pat. No. 3,823,201; particularly incolumns 2-8 and the Examples of U.S. Pat. No. 4,690,956; and in U.S.Pat. No. 4,524,157; all of which patents are herein incorporated byreference.

Non-graft polymer modified polyols are also preferred, for example,those prepared by the reaction of a polyisocyanate with an alkanolaminein the presence of a polyol as taught by U.S. Pat. Nos. 4,293,470;4,296,213; and 4,374,209; dispersions of polyisocyanurates containingpendant urea groups as taught by U.S. Pat. No. 4,386,167; andpolyisocyanurate dispersions also containing biuret linkages as taughtby U.S. Pat. No. 4,359,541. Other polymer modified polyols may beprepared by the in situ size reduction of polymers until the particlesize is less than 20 μm, preferably less than 10 μm.

Suitable polyhydric polythioethers which may be condensed with alkyleneoxides include the condensation product of thiodiglycol or the reactionproduct of a dicarboxylic acid such as is disclosed above for thepreparation of the hydroxyl-containing polyesters with any othersuitable thioether glycol.

The hydroxyl-containing polyester may also be a polyester amide such asis obtained by including some amine or amino alcohol in the reactantsfor the preparation of the polyesters. Thus, polyester amides may beobtained by condensing an amino alcohol such as ethanolamine with thepolycarboxylic acids set forth above or they may be made using the samecomponents that make up the hydroxyl-containing polyester with only aportion of the components being a diamine such as ethylene diamine.

Polyhydroxyl-containing phosphorus compounds which may be used includethose compounds disclosed in U.S. Pat. No. 3,639,542. Preferredpolyhydroxyl-containing phosphorus compounds are prepared from alkyleneoxides and acids of phosphorus having a P₂ O₅ equivalency of from about72 percent to about 95 percent.

Suitable polyacetals which may be condensed with alkylene oxides includethe reaction product of formaldehyde or other suitable aldehyde with adihydric alcohol or an alkylene oxide such as those disclosed above.

Suitable aliphatic thiols which may be condensed with alkylene oxidesinclude alkanethiols containing at least two -SH groups such as1,2-ethanedithiol, 1,2-propanedithiol, 1,2-propanedithiol, and1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; andalkyne thiols such as 3-hexyne-1,6-dithiol.

The ingredient 2-chloropropane is most effective at solubilizingpolyoxyalkylene polyether polyols. We have discovered that2-chloropropane only partially homogeneously solubilizes C₄ -C₆aliphatic hydrocarbons in polyester polyols. Some commercially availablepolyester polyols contain additives such as nonyl phenols which renderthe C₄ -C₆ aliphatic hydrocarbons more soluble in the presence of2-chloropropane. Nevertheless, optimum miscibility is obtained in thepresence of polyoxyalkylene polyether polyols. For this reason, the a)compounds preferably contain greater than 50 weight percent ofpolyoxyalkylene polyether polyols. It is more preferred that thecompounds having at least two isocyanate reactive hydrogens consistessentially of polyoxyalkylene polyether polyols, meaning that 20 weightpercent or less of the polyols are other than polyoxyalkylene polyetherpolyols such as polyester polyols, and most preferably, 100 weightpercent of the compounds are polyoxyalkylene polyether polyols.

The second essential ingredient in the combination is 2-chloropropane,which not only acts to solubilize the C₄ -C₆ aliphatic hydrocarbon, butis also a coblowing agent. Thus, the amount of C₄ -C₆ aliphatichydrocarbon blowing agent used, along with any additional optionalco-blowing agents used, may be reduced by the molar equivalent producedby the blowing action of 2-chloropropane. The amount of 2-chloropropaneused in the polyol composition is effective to homogeneously solubilizethe C₄ -C₆ aliphatic hydrocarbon in the a) compounds. The particularamount will vary depending upon the amount of C₄ -C₆ aliphatichydrocarbon used and the type and amounts of polyoxyalkylene polyetherpolyols used. It is preferred, however, to use the minimum amount of2-chloropropane necessary to render the C₄ -C₆ aliphatic hydrocarbonhomogeneously miscible in the particular polyol composition used to makethe rigid foam. Suitable amounts of 2-chloropropane will generally rangefrom 2 pbw to 10 pbw, more preferably from 6 pbw to 8 pbw, based on 100pbw of the total amount of polyoxyalkylene polyether polyols used.

Examples of the c) aliphatic C₄ -C₆ hydrocarbons include linear orbranched alkanes, e.g. butane, isobutane, 2,3 dimethylbutane, n- andisopentane and technical-grade pentane mixtures, and n- and isohexanes.Preferred are n-pentane, isopentane or n-hexane, or a mixture thereof.Furthermore, specific examples of alkenes are 1-pentene, 2-methylbutene,3-methylbutene, and 1-hexene; and of cycloalkanes are cyclobutane,preferably cyclopentane, cyclohexane or mixtures thereof.Preferentially, cyclopentane, n- and isopentane, n-hexane, and mixturesthereof are employed.

The blowing agents which can be used in addition to the mono-halogenatedhydrocarbon may be divided into the chemically active blowing agentswhich chemically react with the isocyanate or with other formulationingredients to release a gas for foaming, and the physically activeblowing agents which are gaseous at the exotherm foaming temperatures orless without the necessity for chemically reacting with the foamingredients to provide a blowing gas. Included with the meaning ofphysically active blowing agents are those gases which are thermallyunstable and decompose at elevated temperatures.

Examples of chemically active blowing agents are preferentially thosewhich react with the isocyanate to liberate gas, such as CO₂. Suitablechemically active blowing agents include, but are not limited to, water,mono- and polycarboxylic acids having a molecular weight of from 46 to300, salts of these acids, and tertiary alcohols.

Water is preferentially used as a co-blowing agent. Water reacts withthe organic isocyanate to liberate CO₂ gas which is the actual blowingagent. However, since water consumes isocyanate groups, an equivalentmolar excess of isocyanate must be used to make up for the consumedisocyanates.

The organic carboxylic acids used are advantageously aliphatic mon- andpolycarboxylic acids, e.g. dicarboxylic acids. However, other organicmono- and polycarboxylic acids are also suitable. The organic carboxylicacids may, if desired, also contain substituents which are inert underthe reaction conditions of the polyisocyanate polyaddition or arereactive with isocyanate, and/or may contain olefinically unsaturatedgroups. Specific examples of chemically inert substituents are halogenatoms, such as fluorine and/or chlorine, and alkyl, e.g. methyl orethyl. The substituted organic carboxylic acids expediently contain atleast one further group which is reactive toward isocyanates, e.g. amercapto group, a primary and/or secondary amino group, or preferably aprimary and/or secondary hydroxyl group.

Suitable carboxylic acids are thus substituted or unsubstitutedmonocarboxylic acids, e.g. formic acid, acetic acid, propionic acid,2-chloropropionic acid, 3-chloropropionic acid, 2,2-dichlorpropionicacid, hexanoic acid, 2-ethyl-hexanoic acid, cyclohexanecarboxylic acid,dodecanoic acid, palmitic acid, stearic acid, oleic acid,3-mercapto-propionic acid, glycol acid, 3-hydroxypropionic acid, lacticacid, ricinoleic acid, 2-aminopropionic acid, benzoic acid,4-methylbenzoic acid, salicylic acid and anthranilic acid, andunsubstituted or substituted polycarboxylic acids, preferablydicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid,fumaric acid, maleic acid, glutaric acid, adipic acid, sebacic acid,dodecanedioic acid, tartaric acid, phthalic acid, isophthalic acid andcitric acid. Preferable acids are formic acid, propionic acid, aceticacid, and 2-ethylhexanoic acid, particularly formic acid.

The amine salts are usually formed using tertiary amines, e.g.triethylamine, dimethylbenzylamine, diethylbenzylamine,triethylenediamine, or hydrazine. Tertiary amine salts of formic acidmay be employed as chemically active blowing agents which will reactwith the organic isocyanate. The salts may be added as such or formed insitu by reaction between any tertiary amine (catalyst or polyol) andformic acid contained in the polyol composition.

Combinations of any of the aforementioned chemically active blowingagents may be employed, such as formic acid, salts of formic acid,and/or water.

Physically active blowing agents are those which boil at the exothermfoaming temperature or less, preferably at 50° C. or less. The mostpreferred physically active blowing agents are those which have an ozonedepletion potential of 0.05 or less. Examples of physically activeblowing agents besides the C₄ -C₆ aliphatic hydrocarbons mentioned aboveare hydrochlorofluorocarbons (HCFCs); hydrofluorocarbons (HFCs);perfluorinated hydrocarbons (HFCs); fluorinated ethers (HFCs); anddecomposition products.

Any hydrochlorofluorocarbon blowing agent may be used in the presentinvention. Preferred hydrochlorofluorocarbon blowing agents include1-chloro-l,2-difluoroethane; 1-chloro-2,2-difluoroethane (142a);1-chloro-l,l-difluoroethane (142b); 1,1-dichloro-1-fluoroethane (141b);1-chloro-1,1,2-trifluoroethane; 1-chloro-l,2,2-trifluoroethane;1,1-dichloro-1,2-difluoroethane; 1-chloro-1,1,2,2-tetrafluoroethane(124a); 1-chloro-1,2,2,2-tetrafluoroethane (124);1,1-dichloro-1,2,2-trifluoroethane; 1,1-dichloro-2,2,2-trifluoroethane(123); and 1,2-dichloro-1,1,2-trifluoroethane (123a);monochlorodifluoromethane (HCFC-22); 1-chloro-2,2,2-trifluoroethane(HCFC-133a); gem-chlorofluoroethylene (R-1131a);chloroheptafluoropropane (HCFC-217); chlorodifluoroethylene (HCFC- 1122); and transchlorofluoroethylene (HCFC-1131). The most preferredhydrochlorofluorocarbon blowing agent is 1,1-dichloro-l-fluoroethane(HCFC-141b).

Suitable hydrofluorocarbons, perfluorinated hydrocarbons, andfluorinated ethers include difluoromethane (HFC-32);1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1-difluoroethane (HFC-152a ); 1,2-difluoroethane (HFC-142),trifluoromethane; heptafluoropropane; 1,1,1-trifluoroethane;1,1,2-trifluoroethane; 1,1,1,2,2-pentafluoropropane;1,1,1,3-tetrafluoropropane; 1,1,2,3,3-pentafluoropropane;1,1,1,3,3-pentafluoro-n-butane; hexafluorocyclopropane (C-216);octafluorocyclobutane (C-318); perfluorotetrahydrofuran; perfluoroalkyltetrahydrofurans; perfluorofuran; perfluoro-propane,-butane,-cyclobutane, -pentane,-cyclopentane, and -hexane, -cyclohexane,-heptane, and octane; perfluorodiethyl ether; perfluorodipropyl ether;and perfluoroethyl propyl ether.

Decomposition type physically active blowing agents which release a gasthrough thermal decomposition include pecan flour, amine/carbon dioxidecomplexes, and alkyl alkanoate compounds, especially methyl and ethylformates.

Polyisocyanate based foam densities typical for many applications rangefrom free rise demities of 0.5 to 10 pcf, preferably from 1.2 to 3.5pcf. The amount by weight of all blowing agents is generally, based on100 pbw of the a) compounds, from 0.05 to 45 pbw. The C₄ -C₆ aliphatichydrocarbon is preferably the chief density controlling agent, meaningthat greater than 50 mole percent of the gases produced for blowing areC₄ -C₆ aliphatic hydrocarbons. In general the amount of c) hydrocarbonis from 10 to 35 pbw based on 100 pbw of the a) compounds, morepreferably from 20 pbw to 30 pbw.

Water is typically found in minor quantities in the polyols as abyproduct and may be sufficient to provide the desired blowing from achemically active substance. Preferably, however, water is additionallyintroduced into the polyol composition in amounts from 0.05 to 5 pbw,preferably from 0.25 to 3 pbw, based on 100 pbw of the a) compounds. Thephysically active blowing agents, if employed, make up the remainder ofthe blowing agent for a total of from 0.05 to 45 pbw.

Besides the polyols in the polyol composition, and the blowing agents,there may also be included crosslinkers/chain extenders, surfactants,non-reactive (additive) organophosphorus flame retardants and othertypes of flame retardants, catalysts, dyes and pigments, fillers,anti-hydrolysis agents, and fungistatic and bacteriostatic agents.

Chain-extending agents which have no polyether or polyester groups mayoptionally be employed in the preparation of the polyurethane foamsinclude those compounds having at least two functional groups bearingactive hydrogen atoms and with number average molecular weights of lessthan 400, more preferably 46 to 300, such as water, hydrazine, primaryand secondary diamines, amino alcohols, amino acids, hydroxy acids,glycols, or mixtures thereof. The weight of the chain extending agentsare included as a pan of the "polyols" for the purpose of calculatingparts by weight of a compound based on 100 pbw of the polyols. Apreferred group of chain-extending agents includes water, ethyleneglycol, 1,3-propanediol, 1,10-decanediol, o,-m,-p-dihydroxycyclohexane,diethylene glycol, 1,6-hexanediol, glycerine, trimethylol propane,1,2,4-, 1,3,5-trihydroxycyclohexane, bis(2hydroxyethyl) hydroquinone,1,4-butanediol and primary and secondary diamines which react morereadily with a prepolymer than does water such as phenylene diamine,1,4-cyclohexane-bis-(methylamine), ethylenediamine, diethylenetriamine,N-(2-hydroxypropyl)ethylenediamine, piperazine, and 2-methylpiperazine.

Examples of suitable suffactants are compounds which serve to supporthomogenization of the starting materials and may also regulate the cellstructure of the plastics. Specific examples are salts of sulfonicacids, e.g., alkali metal salts or ammonium salts of fatty acids such asoleic or stearic acid, of dodecylbenzene- or dinaphthylmethanedisulfonicacid, and ricinoleic acid; foam stabilizers, such assiloxane-oxyalkylene copolymers and other organopolysiloxanes,oxyethylated alkyl-phenols, oxyethylated fatty alcohols, paraffin oils,castor oil esters, ricinoleic acid esters, Turkey red oil and groundnutoil, and cell regulators, such as paraffins, fatty alcohols, anddimethylpolysiloxanes. The surfactants are usually used in amounts of0.01 to 5 parts by weight, based on 100 parts by weight of the a)compounds.

Catalysts may be employed which greatly accelerate the reaction of thecompounds containing hydroxyl groups and with the modified or unmodifiedpolyisocyanates. Examples of suitable compounds are organometalliccompounds, preferably organotin compounds, such as tin(H) salts oforganic carboxylic acids, for example, tin(II) acetate, tin(II)octanoate, tin(II) ethylhexanoate and tin(H) laurate, and thedialkyltin(IV) salts of organic carboxylic acids, for example,dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate anddioctyltin diacetate, and tertiary amines, for example, triethylamine,triethylenediamine, tributylamine, dimethylbenzylamine, N-methyl-,N-ethyl- and N-cyclohexylmorpholine,N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamineor -hexanediamine, N,N,N'-trimethyl isopropyl propylenediamine,pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether,bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2dimethylimidazole,1-azabicylo[3.3.0]octane and preferably 1,4-diazabicylo[2.2.2]octane,and alkanolamine compounds, such as triethanolamine,triisopropanolamine, N-methyl- and N-ethyldiethanolamine anddimethylethanolamine.

Any suitable urethane forming catalyst may be used including tertiaryamines such as, for example, triethylenediamine, N-methylmorpholine,N-ethylmorpholine, diethylethanolamine, N-cocomorpholine,1-methyl-4-dimethylaminoethylpiperazine, 3-methoxypropyldimethylamine,N,N,N'-trimethylisopropyl propylenediamine,3-diethylaminopropyldiethylamine, dimethylbenzylamine, and the like.Other suitable catalysts are, for example, stannous chloride, dibutyltindi-2-ethyl hexanoate, stannous oxide, as well as other organometalliccompounds such as are disclosed in U.S. Pat. No. 2,846,408.

The foams made according to the invention are rigid or semi-rigid and,if used for insulation purposes, are closed celled. By a polyurethanefoam is meant a foam having some polyurethane linkages, such as apolyurethane (PU) foam where polyurethane linkages predominate, apolyurethane-polyisocyanurate (PU-PIR) foam where there exists asignificant number of polyurethane and polyisocyanurate linkages, andpolyisocyanurate (PIR) foams where the polyisocyanurate linkagespredominate over the polyurethane linkages; but nevertheless,polyurethane linkages are present. To prepare the polyurethane foamscontaining a predominant number of isocyanurate linkages, apolyisocyanurate catalyst is employed. Suitable polyisocyanuratecatalysts are alkali salts, for example, sodium salts, preferablypotassium salts and ammonium salts, of organic carboxylic acids,expediently having from 1 to 8 carbon atoms, preferably 1 or 2 carbonatoms, for example, the salts of formic acid, acetic acid, propionicacid, or octanoic acid, and tris(dialkylaminoethyl)-,tris(dimethylamninopropyl)-, tris(dimethylaminobutyl)- and thecorresponding tris(diethylaminoalkyl)-s-hexahydrotriazines. However,(trimethyl-2-hydroxypropyl)ammonium formate,(trimethyl-2-hydroxypropyl)ammonium octanoate, potassium acetate,potassium formate and tris(diemthylaminopropyl )-s-hexahydrotriazine arepolyisocyanurate catalysts which are generally used. The suitablepolyisocyanurate catalyst is usually used in an amount of from 1 to 10parts by weight, preferably form 1.5 to 8 parts by weight, based on 100parts by weight of the total mount of a) compounds.

Other suitable catalysts may optionally be employed in addition to thetertiary amine catalysts mentioned above. For example, tin catalysts maybe used to shorten tack time and promote green strength. Suitableorganotin tin catalysts are tin (II) salts of organic carboxylic acids,e.g., tin (II) acetate, tin (II) octanoate, tin (II) ethylhexanoate andtin (II) laurate, and dialkyltin (IV) salts of organic carboxylic acids,e.g., dibutyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate,dibutyltin maleate, and dioctyltin diacetate. Preferred, however, aretin catalysts with tin-sulfur bonds which are resistant to hydrolysis,such as dialkyltin dimercaptides, including dimethyl-, dibutyl-, anddioctyl- tin dimercaptides.

Examples of suitable additive flameproofing agents are tricresylphosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl)phosphate, and tris(2,3-dibromopropyl) phosphate.

In addition to the above-mentioned halogen-substituted phosphates, it isalso possible to use inorganic or organic flameproofing agents, such asred phosphorus, aluminum oxide hydrate, antimony trioxide, arsenicoxide, ammonium polyphosphate (Exolit®) and calcium sulfate, expandablegraphite or cyanufic acid derivatives, e.g., melamine, or mixtures oftwo or more flameproofing agents, e.g., ammonium polyphosphates andmelamine, and, if desired, corn starch, or ammonium polyphosphate,melamine, and expandable graphite and/or, if desired, aromaticpolyesters, in order to flameproof the polyisocyanate polyadditionproducts. In general, from 2 to 50 parts by weight, preferably from 5 to25 parts by weight, of said flameproofing agents may be used per 100parts by weight of the a) compounds.

For the purposes of the invention, fillers are conventional organic andinorganic fillers and reinforcing agents. Specific examples areinorganic fillers, such as silicate minerals, for example,phyllosilicates such as antigorite, serpentine, hornblendes, amphiboles,chrysotile, and talc; metal oxides, such as kaolin, aluminum oxides,titanium oxides and iron oxides; metal salts, such as chalk, baryte andinorganic pigments, such as cadmium sulfide, zinc sulfide and glass,inter alia; kaolin (china clay), aluminum silicate and coprecipitates ofbarium sulfate and aluminum silicate, and natural and synthetic fibrousminerals, such as wollastonite, metal, and glass fibers of variouslengths. Examples of suitable organic fillers are carbon black,melamine, colophony, cyclopentadienyl resins, cellulose fibers,polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, andpolyester fibers based on aromatic and/or aliphatic dicarboxylic acidesters, and in particular, carbon fibers.

The inorganic and organic fillers may be used individually or asmixtures and may be introduced into the polyol composition or isocyanateside in amounts of from 0.5 to 40 percent by weight, based on the weightof all the foaming components (the polyols and the isocyanate); but thecontent of mats, nonwovens and wovens made from natural and syntheticfibers may reach values of up to 80 percent by weight.

The polyol component may be reacted with the organic isocyanate atisocyanate equivalence indices ranging from 95 to 500. The flameretardance of a PU-PIR or a PIR foam is increased as the isocyanateindex increases.

The organic isocyanates include all essentially known aliphatic,cycloaliphatic, araliphatic and preferably aromatic multivalentisocyanates. Specific examples include: alkylene diisocyanates with 4 to12 carbons in the alkylene radical such as 1,12-dodecane diisocyanate,2-ethyl- 1,4-tetramethylene diisocyanate, 2-methyl- 1,5-pentamethylenediisocyanate, 1,4-tetramethylene diisocyanate and preferably1,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates such as1,3- and 1,4-cyclohexane diisocyanate as well as any mixtures of theseisomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane(isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate aswell as the corresponding isomeric mixtures, 4,4'- 2,2'-, and2,4'-dicyclohexylmethane diisocyanate as well as the correspondingisomeric mixtures and preferably aromatic diisocyanates andpolyisocyanates such as 2,4- and 2,6-toluene diisocyanate and thecorresponding isomeric mixtures 4,4'-, 2,4'-, and 2,2'-diphenylmethanediisocyanate and the corresponding isomeric mixtures, mixtures of 4,4'-and 2,4'-diphenylmethane diisocyanates and polyphenylenepolymethylenepolyisocyanates (polymefic MDI), as well as mixtures of polymefic MDIand toluene diisocyanates. The organic di- and polyisocyanates can beused individually or in the form of mixtures.

Frequently, so-called modified multivalent isocyanates, i.e., productsobtained by the partial chemical reaction of organic diisocyanatesand/or polyisocyanates are used. Examples include diisocyanates and/orpolyisocyanates containing ester groups, urea groups, biuret groups,allophanate groups, carbodiimide groups, isocyanurate groups, and/orurethane groups. Specific examples include organic, preferably aromatic,polyisocyanates containing urethane groups and having an NCO content of33.6 to 15 weight percent; preferably 31 to 21 weight percent, based onthe total weight, e.g., with low molecular weight diols, triols,dialkylene glycols, trialkylene glycols, or polyoxyalkylene glycols witha molecular weight of up to 1500; modified 4,4'-diphenylmethanediisocyanate or 2,4- and 2,6toluene diisocyanate, where examples of di-and polyoxyalkylene glycols that may be used individually or as mixturesinclude diethylene glycol, dipropylene glycol, polyoxyethylene glycol,polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropyleneglycol, and polyoxypropylene polyoxyethylene glycols or -triols.Prepolymers containing NCO groups with an NCO content of 25 to 9 weightpercent, preferably 21 to 14 weight percent, based on the total weightand produced from the polyester polyols and/or preferably polyetherpolyols described below; 4,4'-diphenylmethane diisocyanate, mixtures of2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4,- and/or 2,6-toluenediisocyanates or polymeric MDI are also suitable. Furthermore, liquidpolyisocyanates containing carbodiimide groups having an NCO content of33.6 to 15 weight percent, preferably 31 to 21 weight percent, based onthe total weight, have also proven suitable, e.g., based on 4,4'- and2,4'- and/or 2,2'-diphenylmethane diisocyanate and/or 2,4'- and/or2,6-toluene diisocyanate. The modified polyisocyanates may optionally bemixed together or mixed with unmodified organic polyisocyanates such as2,4'- and 4,4'-diphenylmethane diisocyanate, polymeric MDI, 2,4'- and/or2,6-toluene diisocyanate.

Crude polyisocyanates may also be used in the compositions of thepresent invention, such as crude toluene diisocyanate obtained by thephosgenation of a mixture of toluenediamines or crude diphenylmethaneisocyanate obtained by the phosgenation of crude diphenylmethanediamine. The preferred or crude isocyanates are disclosed in U.S. Pat.No. 3,215,652.

The foams can be prepared batchwise or continuously by the prepolymerprocess or by the one-shot process using conventional low pressure orimpingement mixers. The foam ingredients may be mixed at from 15° to 90°C., preferably at 20° to 35° C., and introduced into an open moldoptionally preheated, or poured or sprayed onto a substrate or into acavity. The foams have applications where insulation is desired such ashome refrigerators, industrial or equipment casings, jackets in hotwater tanks or pipes, and residential and commercial buildinginsulation. Other applications would include sound absorbing foams,energy absorbing foams, and doors.

The foams prepared herein are rigid and preferably closed cell. By aclosed cell polyurethane foam is meant that at least 85% of the cellsare closed. For insulation purposes, it is preferred that greater than90%, more preferably 95% or more of the cells are closed.

The following non-limiting examples illustrate an embodiment of theinvention: .

Polyol A is a polyoxyalkylene polyether polyol comprising the reactionproduct of ethylene glycol and having an OH number of about 240.

Polyol B Terate 2541, a polyester polyol, DMT-initiated.

B-8432 is a silicone surfactant commercially available from GoldschmidtCorporation.

HEXCHEM®977 is potassium octoate, a polyisocyanurate-promoting catalyst.

POLYCAT®5 is pentamethyldiethylenetriamine, a polyurethane-promotingcatalyst commercially available from Air Products.

EXAMPLE I

All of the polyol ingredients listed in Table I were mixed at the statedpans by weight. The amount of 200 grams of the polyol composition except2-chloropropane was placed in each of ten four-ounce glass bottles. Thestated amounts of 2-chloropropane were added to each bottle andthoroughly mixed. The bottles were left to stand for one hour, afterwhich the results tabulated below in Table 2 were observed.

                                      TABLE 1                                     __________________________________________________________________________    INGREDIENTS 1  2  3  4  5  6  7  8  9  10                                     __________________________________________________________________________    POLYOL A    100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- -- -- -- --                                     POLYOL B    -- -- -- -- -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                    B-8432      2  2  2  2  2  2  2  2  2  2                                      HEXCHEM 977 3  3  3  3  3  3  3  3  3  3                                      POLYCAT 5   0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                    WATER       0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                    CYCLCOPENTANE.sup.1                                                                       25 25 25 25 25 25 25 25 25 25                                     2-CHLOROPROPANE                                                                           0  2.5                                                                              5  7.5                                                                              10 0  2.5                                                                              5  7.5                                                                              10                                     __________________________________________________________________________     .sup.1 The cyclopentane used was a mixture of about 70 percent                cyclopentane and 30 percent of pentane isomers.                          

                  TABLE 2                                                         ______________________________________                                        SAMPLES RESULTS                                                               ______________________________________                                        1       0.2 INCH OF CLEAR LIQUID ON TOP,                                              REMAINDER OF LIQUID WAS CLOUDY                                        2       0.1 INCH OF CLEAR LIQUID ON TOP, A                                            MILDLY CLOUDY CENTER PORTION, AND                                             0.2 INCH CLEAR LIQUID ON THE BOTTOM                                           OF JAR.                                                               3       CLOUDY LIQUID WITH 0.5 INCH CLEAR                                             LIQUID AT BOTTOM OF JAR.                                              4       CLEAR LIQUID THROUGHOUT.                                              5       CLEAR LIQUID THROUGHOUT.                                              6       ONE (1) INCH CLEAR LIQUID SEPARATED                                           AT EIGHT (8) HOURS.                                                   7       ONE (1) INCH CLEAR LIQUID SEPARATED                                           AT EIGHT (8) HOURS.                                                   8       ONE (1) INCH CLEAR LIQUID SEPARATED                                           AT TEN (10) HOURS.                                                    9       ONE (1) INCH CLEAR LIQUID SEPARATED                                           AT TEN (10) HOURS.                                                    10      ONE (1) INCH CLEAR LIQUID SEPARATED                                           AT TWELVE (12) HOURS.                                                 ______________________________________                                    

The results indicate that at 25 pbw of the cyclopentane mixture usedbased on 100 pbw of the Polyol A used, 2-chloropropane immediately begansolubilizing some of the cyclopentane mixture (Samples 2-3), andhomogeneously solubilized the cyclopentane mixture at 7.5 and 10 pbw.However, 2-chloropropane did not solubilize the cyclopentane mixture inthe polyester polyol TERATE 2541.

While the cyclopentane mixture was not miscible in TERATE 2541 in thepresence of 2-chloropropane, it is to be understood that the scope ofthe invention only requires the presence of a polyoxyalkylene polyetherpolyol, which polyether polyol may be mixed with other compounds havingisocyanate reactive hydrogens such as polyester polyols, even where themajority of the polyols are polyester polyols because 2-chloropropanewill be effective at solubilizing some of the polyoxyalkylene polyetherpolyols and some modified polyester polyols.

What I claim is:
 1. A process for making a rigid polyisocyanate basedfoam comprising adding 2-chloropropane to a polyoxyalkylene polyetherpolyol and a blowing agent comprising a C₄ -C₆ aliphatic hydrocarbon inan amount effective to homogeneously solubilize said hydrocarbon in saidpolyol to form a homogeneously soluble polyol composition, and reactingsaid homogeneously soluble composition with an organic isocyanate toproduce a rigid polyisocyanate based foam.
 2. The process of claim 1,wherein the amount of 2-chloropropane is from 2 pbw to pbw based on 100pbw of all the polyoxyalkylene polyether polyols.
 3. The process ofclaim 2, wherein the amount of 2-chloropropane is from 6 pbw to 12 pbw.4. The process of claim 2, wherein the c) aliphatic hydrocarboncomprises n-pentane, isopentane, cyclopentane, or mixtures thereof. 5.The process of claim 4, wherein the organic isocyanate comprises4,4'-diphenylmethane diisocyanate, polymethylene polyphenylenepolyisocyanate, or mixtures thereof.
 6. The process of claim 1, whereinsaid homogeneously soluble polyol composition further comprises apolyurethane-promoting catalyst.
 7. The process of claim 1, wherein theamount of said hydrocarbon is from 10 pbw to pbw based on 100 pbw ofsaid polyols.
 8. The process of claim 7, wherein the amount of saidhydrocarbon is from 20 pbw to pbw based on 100 pbw of said polyols.
 9. Aprocess for making a homogeneously soluble polyol composition comprisingadding 2-chloropropane to one or more compounds having at least twoisocyanate active hydrogens comprising a polyoxyalkylene polyetherpolyol and a blowing agent comprising a C₄ -C₆ aliphatic hydrocarboncompound, in an amount effective to homogeneously solubilize saidhydrocarbon in said polyether polyol.
 10. The process of claim 9,wherein the amount of 2-chloropropane is from 2 pbw to pbw based on 100pbw of said polyether polyols.
 11. The process of claim 9, wherein theamount of said hydrocarbon is from 10 pbw to 35 pbw based upon 100 pbwof said compounds having at least two isocyanate active hydrogens. 12.The process of claim 11, wherein the amount of said hydrocarbon is from20 pbw to 30 pbw.
 13. The process of claim 1, wherein said hydrocarboncomprises cyclopentane.
 14. The process of claim 9, wherein saidhydrocarbon comprises cyclopentane.